Bright pink, lavender and blue mineral dyeing single bath process for cellulosics

ABSTRACT

A certain cobalt organic salt was found to produce a water soluble aqueous complex with zirconyl ammonium carbonate, from which an insoluble pink deposit of cobalt and zirconia is deposited on cellulosics by heat. The deposit is bright pink and is completely resistant to hot water washings. The incorporation of varying amounts of copper metaborate into the aqueous cobalt complex produces compatible, uniform, soluble single bath complexes of copper, cobalt, and zirconia which produce lavender to bright blue insoluble deposits on cellulosics by heating (curing). By increasing the ratio of zirconia (ZrO2) to cobalt (Co) by about 7 or 8 to 1, in the bath, lavender to bluish-pink deposits are produced by heat curing without copper. Using low ratios of approximately 1:1 of cobalt and zirconia, produces bright pink mineral pigments on heating (curing), while gradually increasing the copper ratio to cobalt, from 1:1 to 1.5 to 1, produces lavender to bright blue insoluble deposits on heating (curing). The copper containing mineral dyeings on cellulosic are fungicidal and algaecidal. Bright color shades, resistant to light and microorganisms, are desirable for the protection and sales appeal of textiles and other cellulosics.

United States Patent [191 Conner Dec. 18, 11973 [75] Inventor: CharlesJ. Conner, Metairie, La.

[73] Assignee: The United States of America as represented by theSecretary of Agriculture, Washington, DC.

[22] Filed: May 5, 1972 [21] Appl. No.: 250,560

[52] US. Cl 8/52, 8/17, 117/143 R, 424/140 [51] Int. Cl D06p 3/60 [58]Field of Search 8/52, 17; 117/143 R; 424/140 [56] References CitedUNITED STATES PATENTS 3,291,635 12/1966 Conner et a1. ll7/l38.53,431,059 3/1969 Conner et al. 8/52 OTHER PUBLlCATlONS Textile ResearchJournal, Vol. 34, No. 4, 1964, pp. 347-357 Textile Research Journal,Vol. 37, No. 2, 1967, pp. 94-102.

Primary .Examiner-Donald Levy Assistant ExaminerBruce H. HessAttorney-R. Hoffman et al.

[5 7] ABSTRACT A certain cobalt organic salt was found to produce awater soluble aqueous complex with zirconyl ammonium carbonate, fromwhich an insoluble pink deposit of cobalt and zirconia is deposited oncellulosics by heat. The deposit is bright pink and is completelyresistant to hot water washings. The incorporation of varying amounts ofcopper metaborate into the aqueous cobalt complex produces compatible,uniform, soluble single bath complexes of copper, cobalt, and zirconiawhich produce lavender to bright blue insoluble deposits on cellulosicsby heating (curing). By increasing the ratio of zirconia (ZrO to cobalt(Co) by about 7 or 8 to 1, in the bath, lavender to bluish-pink depositsare produced by heat curing without copper. Using low ratios ofapproximately 1:1 of cobalt and zirconia, produces bright pink mineralpigments on heating (curing), while gradually increasing the copperratio to cobalt, from 1:1 to 1.5 to 1, produces lavender to bright blueinsoluble deposits on heating (curing). The copper containing mineraldyeings on cellulosic are fungicidal and algaecidal. Bright colorshades, resistant to light and microorganisms, are desirable for theprotection and sales appeal of textiles and other cellulosics.

12 Claims, No Drawings BRIGHT PINK, LAVENDER AND BLUE MINERAL DYEINGSINGLE BATH PROCESS FOR CELLULOSICS A non-exclusive, irrevocable,royalty-free license in the invention herein described, throughout theworld for all purposes of the United States Government, with the powerto grant sublicenses for such purposes, is hereby granted to theGovernment of the United States of America.

Numerous organic dyes have been known to produce bright shades of pink,lavender, and blue but these materials are not durable tosunlight'exposure on awnings, umbrellas, sails, etc. Most organic colorsare of poor light fastness when used on weatherable fabrics. The textileindustry has long desired attractive bright mineral dye shades thatcould be applied from single bath systems, and which would be resistantto sunlight as a result of their mineral (inorganic) composition. It hadbeen visualized that aqueous complexes of certain metal salts withalkaline zirconyl ammonium carbonate could deposit colored insolubledeposits ofzirconia and the complexed metal salt oxide or other basiccompounds (carbonate, basic acetate, borate, etc.).

Cobalt citrate produces alkaline soluble complexes with ammoniumhydroxide and ammonium carbonate, as well as zirconyl ammoniumcarbonate. Hydrated zirconia is a sunlight screener and algaecide andlocks other metal ions onto cellulosics. Consequently, thesolubilization of cobalt citrate in z'irconyl ammonium carbonateproduces an alkaline complex of both cobalt and zirconia from which thecobalt-zirconia deposit, by heating, is a bright pink mineral pigmentdeposit, resistant to leaching and water washing, and being mineral innature, free of organics after washing, resistant to light and algae,and resistant to both algae and fungi when formulated with copper.

The dye shades of pink, lavender, and blue are very bright andattractive, and desirable for mineral dyeing textiles and paper(cellulosics).

The main object of the invention is to provide a single bath aqueoussystem which can be used to dye cellulosics a bright shade of pink,lavender, or blue with mineral pigments having light screening,algaecidal, and fungicidal properties.

A second object of the invention is to provide bright shades of mineraldyeings, comparable to organic dyeings, but being of mineral compositionfor resistance to light, microorganisms, and weathering.

A third object of the invention is to shorten conventional mineraldyeing procedures to a simple pad, dry, and cure process where thefungicidal component contributes to the color shade produced and thezirconia furnishes algaecidal properties.

A fourth object of the invention is to provide a new and unique methodto lock cobalt pink deposits onto cellulosics by a single bathapplication.

A fifth object of the invention is to provide a unique single bathsystem for applying cobalt, copper and other metal salts with zirconiato cellulosics by merely wetting and heating.

The prior art teaches that pink, lavender, and blue cellulosic dyeings,of bright shade, are best accomplished with organic dyes, applied byvarious and numerous processing steps. It also teaches that these samebright colors fade rapidly in direct sunlight and are not suitable foroutdoor use. The prior art also teaches that cobalt and copper mineraldyeings must be applied to cellulosics by double decomposition, followedby washings and further dryings, with fungicide added by separateprocessing. The present invention shows that cobalt and combinations ofcobalt, copper, and zirconia, can be applied to cellulosics from asingle bath system by merely pad, dry, cure and wash processing, wherethe mineral deposit constitutes the mineral color (dye), fungicide,algaecide and light screener. The same bath system can be modified withcopper to give any desired shade of pink. lavender or bright blue, bymaking more or less additions of copper metaborate to the cobaltzirconylammonium carbonate single bath system.

The bath system, so produced, is stable for paddings and produces thedyeing when wetted onto the cellulosic and drying on same, followed byheating to a conventional oven temperature of 150C-l55C for a fewminutes (2 to 3). Hot water washing does not affect the dyeing, which isstable, uniform, and bright.

Thus, a pad bath formulation consisting of about 2 to 5 parts of cobaltcitrate, about 10 to 48 parts of a zirconyl ammonium carbonate solutioncontaining about 10 weight percent zirconium dioxide, and about 40 toparts water will effect the pink coloration of cellulosic fabrics. Inuse, a cellulosic fabric is padded with said formulation, the paddedfabric dried at 120 C., for about 2 to 3 minutes, the dried fabric thencured at 130 C., for about 2 to 3 minutes, the cured fabric washed, andthe cured, washed fabric finally dired at 130 C., for about 2 to 3minutes.

A pad bath formulation consisting of about 2 to 5 parts of cobaltcitrate and about to 96 parts of a zirconyl ammonium carbonate solutioncontaining about 10 weight percent zirconium dioxide will effect thelavender coloration of cellulosic fabrics. In use, a cellulosic fabricis padded with said formulation, the padded fabric dried at C., forabout 2 to 3 minutes, the dried fabric then cured at C., for about 2 3minutes, the cured fabric washed, and the cured, washed fabric finallydried at 130 C., for about 2 to 3 minutes.

A pad bath formulation consisting of about 3 to 5 parts of cobaltcitrate, about 0.5 to 1.0 part copper metaborate, about 90 to 95 partscarbonate solution containing about 10 weight percent zirconium of azirconly ammonium/dioxide, and about 0.5 to 1.5 parts ammonium carbonatewill effect the lavender-blue coloration of cellulosic fabrics and will,in addition, confer fungicidal properties to said cellulosic fabrics. Inuse, a cellulosic fabric is padded with said formulation, the paddedfabric dried at 130 C., for about 2 to 3 minutes, the dried fabric thencured at 150 C. to 1550 C., for about 3 to 4 minutes, the cured fabricwashed, and the cured, washed fabric finally dired at 130 C. to C., forabout 3 to 4 minutes.

A pad bath formulation consisting of about 3 to 8 parts of cobaltcitrate, about 2 to 2.5 parts copper metaborate, about 90 to 95 parts ofa zirconyl ammonium carbonate solution containing about 10 weightpercent zirconium dioxide, and about 0.5 to 1.5 parts of ammoniumcarbonate will effect the purple-blue coloration of cellulosic fabricsand will, in addition, confer fungicidal properties to said cellulosicfabrics. In use, a cellulosic fabric is padded with said formulation,the padded fabric dried at 130 C., for about 2 to 3 minutes, the driedfabric then cured at C. to C., for about 3 to 4 minutes, the curedfabric washed, and the cured, washed fabric finally dried at 130 C. to140 C., for about 3 to 4 minutes.

A pad bath formulation consisting of about 3 to parts of cobalt citrate,about 3 to 5 parts copper metaborate, about 90 to 94 parts of a zirconylammonium carbonate solution containing about weight percent zirconiumdioxide, and about 1.0 part ammonium carbonate will effect the bluecoloration of cellulosic fabrics and will, in addition, conferfungicidal properties to said cellulosic fabrics. In use, a cellulosicfabric is padded with said formulation, the padded fabric dried at 130C., for about 2 to 3 minutes, the dried fabric then cured at 150C. to155 C., for about 3 to 4 minutes, the cured fabric washed, and thecured, washed fabric finally dried at 130 C. to 140 C., for about 3 to 4minutes.

A pad bath formulation consisting of about 2 to 4 parts of cobaltcitrate, about 0.5 to 1.0 part copper metaborate, about 10 to 48 partsof a zirconyl ammonium carbonate solution containing about 10 weightpercent zirconium dioxide, about 40 to 75 parts water, and about 5 partsammonium hydroxide will effect the pink coloration of cellulosic fabricsand will, in addition, confer fungicidal properties to said cellulosicfabrics. In use, a cellulosic fabric is padded with said formulation,the padded fabric dried at about 120, for about 2 to 3 minutes, thedried fabric then cured at about 130 C., for about 2 to 3 minutes, thecured fabric washed, and the cured, washed fabric finally dired at about120 C., for about 2 to 3 minutes.

Utility of the invention is obviously in the field of textile dyeing anddyeing of other cellulosics (paper and wood). It is recommended fornon-weatherable goods and also outdoor weatherable goods of a cellulosicnature, such as awnings, tents, umbrellas, sails, shoe lining, boatcovers, apparel, canvas shoes, writing paper, wall paper, tarpaulins,rope, jackets, socks, upholstery, paper bags, hats, etc.

The following examples are presented to illustrate the invention andcertain aspects of its usefulness. These are not to be interpreted aslimiting the invention in any manner whatever. The treatments wereapplied to leather, wood, and paper and are not restricted tocellulosics alone. Porous ceramics dipped into the baths and oven driedand cured, were also mineraldyed the respective color shades.

EXAMPLE 1 One gram (1.0) of cobalt citrate, having the formula of CO (CH O )"6H O was weighed into a 250 ml beaker and mixed with 34.0 grams ofdistilled water. The salt was practically insoluble on stirring. To thismix was added 10.0 grams of zirconyl ammonium carbonate, and stirringcontinued for 5 minutes. A large percentage, approximately 98% (0.98 gm)of the salt dissolves on stirring to produce an aqueous cobaltzirconiacomplex.

EXAMPLE 2 The clear aqueous complex from Example 1 was poured into adish and used to wet a piece of scoured 9 Oz army duck, 4 X 4 inches.The wetted duck was blotted free of excess liquid and oven dried at 130Cfor 2 minutes, followed by an oven cure of 140C (2 minutes). The samplewas dyed pink. The pink sample was hot tap water (55C) washed for 5minutes, followed by oven drying at 130C/2 min. The sample shows no lossof color and remains dyed a bright shade of pink.

EXAMPLE 3 Examples 1 and 2 were repeated with 5.0 grams of ammoniumhydroxide (29.4% NH added to the bath to produce percent solubility ofthe cobalt citrate. The results were the same as with Examples 1 and 2and bright pink mineral dyeings resulted.

EXAMPLE 4 Example 3 was repeated with the cure temperature of the wettedduck being carried out at C instead of 140C. A slightly deeper andbrigher pink" dyeing resulted.

EXAMPLE 5 Two grams (2.0) of coblat citrate was mixed with 38.0 grams ofwater, 10 grams of zirconyl ammonium carbonate (10% ZrO and 5 grams ofammonium hydroxide (29.4% NH to give 55 grams of bath. The bath wasclear and brownish pink, showing complete solubility. Example 2 wasrepeated with this bath. A deep pink" mineral dyeing was produced, whichwas not effected by hot tap water washing.

EXAMPLE 6 Two grams (2.0) of cobalt citrate was mixed with 48.0 grams ofzirconyl ammonium carbonate 10% Zr0 and stirred for 10 minutes until allof the salt dissolves. A clear deep pink bath solution resulted. Thebath contains 9.6% Zr0 and 0.48% Co since cobalt citrate containsapproximately 12% cobalt as metal. This single bath complex (highzirconium) is capable of producing lavender" mineral dyeings.

EXAMPLE 7 The clear bath from Example 6 was used to wet a 4 X 8 inchsample of scoured 9 oz army duck. The thoroughly wetted duck was blottedfree of excess liquid and oven dried at 130C/2 minutes, followed by ovencuring at C/3 minutes. The cured fabric appears violet prior to wash.The cured sample was washed 5 minutes in hot running tap water, becomingbluish-pink It was then oven-dried at 130C for 4 minutes, producing apure bright lavender" mineral dyed fabric.

EXAMPLE 8 EXAMPLE 9 The clear bath from Example 8 was used to wet a 9 X8 inch sample of 9 oz scoured army duck which was blotted free of excessliquid and oven dried at 130C/2 minutes, followed by an oven cure of155C/3 minutes. The freshly cured fabric was purple" in color. It wasthen hot tap water washed for 5 minutes and then oven dried at 130C/4minutes. A bright lavender (bluish) mineral dyeing resultedQ EXAMPLE Thebath prepared in Example 8 was modified to include 1.0 grams of coppermetaborate with 2.0 to 4.0 grams cobalt citrate and 45 to 47.0 grams ofzirconyl ammonium carbonate (10% ZrO Drying, curing, and washingprocedures were followed as in Example 9 with scoured duck. Alavender-purple mineral dyeing resulted.

EXAMPLE 1 1 EXAMPLE 12 The clear bath from Example 11 was applied to a 9inch X 8 inch section of scoured army duck, which was blotted, and ovendried at 130C/2 minutes, followed by oven cure at 155C/3 minutes. A bluedyed fabric resulted. The cured sample was hot tap water washed for 5minutes, followed by oven drying at 130C/4 minutes. A bright bluemineral dyed fabric resulted.

EXAMPLE 13 Example 8 bath was again prepared and applied to a 4 X 8 inchsample of scoured 9 oz army duck. The fabric was oven dried at 120C/2minutes and oven cured at 140C/2 minutes, followed by 5 minutes hot tapwash and oven dry at 120C/2 minutes. The color shade was bluish-pink andcontains copper fungicide.

EXAMPLE 14 Examples 1, 3, 4, 5, 6, 8, 10, 11 were repeated and appliedto filter paper and porous wooden splints. In each instance, apink-lavender-blue mineral dyeing was produced in cure at 150C.

EXAMPLE 15 Examples 2, 7, 9, 10, and 12 were repeated with oven dryingat 120C, followed by cures at 130C/3 minutes, instead of drying at 130Cand curing at 155C. The color shades were lighter and brighter, beingmore of a pestel pink-lavender-blue in each instance. The higher curetemperature of 155C produces deeper and darker color shades.

EXAMPLE 16 Fabrics treated by Examples 2, 5, 7, 9, and 12 were exposedto outdoor sunlight and weather for one week (to be reused as exposuretime is lengthened). The dyeings were exposed to severe weatherconditions of frequent rain followed by sunlight and high temperatureswithout significant color changes or evidence of fading. No growths ofmildew or algae were detected.

EXAMPLE 17 Fabrics (duck) treated in Example 9, 10, and 12 were exposedto soil burial with plain scoured (untreated) duck. After 2 weeks, theuntreated duck showed no retained strength (disintegrated), while theExample 9, 10, and 12 treated samples were intact and not degraded.

I claim:

I. A single bath mineral dyeing process for producing a pink cellulosicfabric, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 2 to5 parts of cobalt citrate, about 10 to 48 parts of a zirconyl ammoniumcarbonate solution containing about 10 weight percent zirconium dioxide,and about 40 to parts water,

b. drying the fabric from (a) at 120C for about 2 to 3 minutes,

c. curing the fabric from (b) at 130C for about 2 to 3 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at 130C for about 2 to 3 minutes.

2. A pad bath formulation for producing a pink cellulosic fabric, saidbath consisting of about 2 to 5 parts of cobalt citrate, about 10 to 48parts of a zirconyl ammonium carbonate solution containing about 10weight percent zirconium dioxide, and about 40 to 75 parts water.

3. A single bath mineral dyeing process for producing a lavendercellulosic fabric, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 2 to5 parts of cobalt citrate and about to 96 parts of a zirconyl ammoniumcarbonate solution containing about 10 weight percent zirconium dioxide,

b. drying the fabric from (a) at C for about 2 to 3 minutes,

0. curing the fabric from (b) at C for about 2 to 3 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at 130C. for about 2 to 3 minutes.

4. A pad bathformulation for producing a lavender cellulosic fabric,said bath consisting of about 2 to 5 parts of cobalt citrate and about90 to 96 parts of a zirconyl ammonium carbonate solution containingabout 10 weight percent zirconium dioxide.

5. A single bath mineral dyeing process for producing a lavender-bluecellulosic fabric with fungicidal properties, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 3 to5 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate,about 90 to 95 parts of zirconyl ammonium carbonate solution containingabout 10 weight percent zirconium dioxide, and about 0.5 to 1.5 partsammonium carbonate,

b. drying the fabric from (a) at 130C for about 2 to 3 minutes,

c. curing the fabric from (b) at C-l55C for about 3 to 4 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at 130C-140C for about 3 to 4 minutes.

6. A pad bath formulation for producing a lavenderblue cellulosic fabricwith fungicidal properties, said bath consisting of about 3 to 5 partsof cobalt citrate, about 0.5 to 1.0 part copper metaborate, about 90 to95 parts of a zirconyl ammonium carbonate solution containing about 10weight percent zirconium dioxide, and about 0.5 to 1.5 parts ammoniumcarbonate.

7. A single bath mineral dyeing process for producing a purple-bluecellulosic fabric with fungicidal properties, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 3 to8 parts of cobalt citrate, about 2 to 2.5 parts copper metaborate, about90 to 95 parts of a zirconyl ammonium carbonate solution containingabout 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts ofammonium carbonate,

b. drying the fabric from (a) at 130C for about 2 to 3 minutes,

0. curing the fabric from (b) at about l50l 55C for about 3 to 4minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at about l30140C for about 3 to 4 minutes.

8. A pad bath formulation for producing a purpleblue cellulosic fabricwith fungicidal properties, said bath consisting of about 3 to 8 partsof cobalt citrate, about 2 to 2.5 parts copper metaborate, about 90 to95 parts of a zirconyl ammonium carbonate solution containing about 10weight percent zirconium dioxide, and about 0.5 to 1.5 parts of ammoniumcarbonate.

9. A single bath mineral dyeing process for producing a blue cellulosicfabric with fungicidal properties, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 3 toparts of cobalt citrate, about 3 to 5 parts copper metaborate, about 90to 94 parts of a zirconyl ammonium carbonate solution containing aboutweight percent zirconium dioxide, and about 1.0 part ammonium carbonate,

b. drying the fabric from (a) at about 130C for about 2 to 3 minutes,

c. curing the fabric from (b) at about l50l55C.

for about 3 to 4 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at about l30-l40C for about 3 to 4minutes.

10. A pad bath formulation for producing a blue cellulosic fabric withfungicidal properties, said bath consisting of about 3 to 5 parts ofcobalt citrate, about 3 to 5 parts copper metaborate, about to 94 partsof a zirconyl ammonium carbonate solution containing about 10 weightpercent zirconium dioxide, and about 1.0 part ammonium carbonate.

1]. A single bath mineral dyeing process for producing a pink cellulosicfabric with fungicidal properties, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 2 to4 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate,about 10 to 48 parts of a zirconyl ammonium carbonate solutioncontaining about 10 weight percent zirconium dioxide, about 40 to 75parts water, and about 5 parts ammonium hydroxide,

b. drying the fabric from (a) at about C for about 2 to 3 minutes,

c. curing the fabric from (b) at about l30C for about 2 to 3 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at about 120C for about 2 to 3 minutes.

12. A pad bath formulation for producing a pink cellulosic fabric withfungicidal properties, said bath consisting of about 2 to 4 part ofcobalt citrate, about 0.5 to 1.0 parts copper metaborate, about 10 to 48parts of a zirconyl ammonium carbonate solution containing about 10weight percent zirconium dioxide, about 40 to 75 parts water, and about5 parts ammonium hydroxide.

2. A pad bath formulation for producing a pink cellulosic fabric, saidbath consisting of about 2 to 5 parts of cobalt citrate, about 10 to 48parts of a zirconyl ammonium carbonate solution containing about 10weight percent zirconium dioxide, and about 40 to 75 parts water.
 3. Asingle bath mineral dyeing process for producing a lavender cellulosicfabric, which process comprises: a. padding a cellulosic fabric with asolution consisting of about 2 to 5 parts of cobalt citrate and about 90to 96 parts of a zirconyl ammonium carbonate solution containing about10 weight percent zirconium dioxide, b. drying the fabric from (a) at120*C for about 2 to 3 minutes, c. curing the fabric from (b) at 130*Cfor about 2 to 3 minutes, d. washing the fabric from (c), and e. dryingthe fabric from (d) at 130*C. for about 2 to 3 minutes.
 4. A padbathformulation for producing a lavender cellulosic fabric, said bathconsisting of about 2 to 5 parts of cobalt citrate and about 90 to 96parts of a zirconyl ammonium carbonate solution containing about 10weight percent zirconium dioxide.
 5. A single bath mineral dyeingprocess for producing a lavender-blue cellulosic fabric with fungicidalproperties, which process comprises: a. padding a cellulosic fabric witha solution consisting of about 3 to 5 parts of cobalt citrate, about 0.5to 1.0 part copper metaborate, about 90 to 95 parts of zirconyl ammoniumcarbonate solution containing about 10 weight percent zirconium dioxide,and about 0.5 to 1.5 parts ammonium carbonate, b. drying the fabric from(a) at 130*C for about 2 to 3 minutes, c. curing the fabric from (b) at150*C-155*C for about 3 to 4 minutes, d. washing the fabric from (c),and e. drying the fabric from (d) at 130*C-140*C for about 3 to 4minutes.
 6. A pad bath formulation for producing a lavender-bluecellulosic fabric with fungicidal properties, said bath consisting ofabout 3 to 5 parts of cobalt citrate, about 0.5 to 1.0 part coppermetaborate, about 90 to 95 parts of a zirconyl ammonium carbonatesolution containing about 10 weight percent zirconium dioxide, and about0.5 to 1.5 parts ammonium carbonate.
 7. A single bath mineral dyeingprocess for producing a purple-blue cellulosic fabric with fungicidalproperties, which process comprises: a. padding a cellulosic fabric witha solution consisting of about 3 to 8 parts of cobalt citrate, about 2to 2.5 parts copper metaborate, about 90 to 95 parts of a zirconylammonium carbonate solution containing about 10 weight percent zirconiumdioxide, and about 0.5 to 1.5 parts of ammonium carbonate, b. drying thefabric from (a) at 130*C for about 2 to 3 minutes, c. curing the fabricfrom (b) at about 150*-155*C for about 3 to 4 minutes, d. washing thefabric from (c), and e. drying the fabric from (d) at about 130*-140*Cfor about 3 to 4 minutes.
 8. A pad bath formulation for producing apurple-blue cellulosic fabric with fungicidal properties, said bathconsisting of about 3 to 8 parts of cobalt citrate, about 2 to 2.5 partscopper metaborate, about 90 to 95 parts of a zirconyl ammonium carbonatesolution containing about 10 weight percent zirconium dioxide, and about0.5 to 1.5 parts of ammonium carbonate.
 9. A single bath mineral dyeingprocess for producing a blue cellulosic fabric with fungicidalproperties, which process comprises: a. padding a cellulosic fabric witha solution consisting of about 3 to 5 parts of cobalt citrate, about 3to 5 parts copper metaborate, about 90 to 94 parts of a zirconylammonium carbonate solution containing about 10 weight percent zirconiumdioxide, and about 1.0 part ammonium carbonate, b. drying the fabricfrom (a) at about 130*C for about 2 to 3 minutes, c. curing the fabricfrom (b) at about 150*-155*C. for about 3 to 4 minutes, d. washing thefabric from (c), and e. drying the fabric from (d) at about 130-140*Cfor about 3 to 4 minutes.
 10. A pad bath formulation for producing ablue cellulosic fabric with fungicidal properties, said bath consistingof about 3 to 5 parts of cobalt citrate, about 3 to 5 parts coppermetaborate, about 90 to 94 parts of a zirconyl ammonium carbonatesolution containing about 10 weight percent zirconium dioxide, and about1.0 part ammonium carbonate.
 11. A single bath mineral dyeing processfor producing a pink cellulosic fabric with fungicidal properties, whichprocess comprises: a. padding a cellulosic fabric with a solutionconsisting of about 2 to 4 parts of cobalt citrate, about 0.5 to 1.0part copper metaborate, about 10 to 48 parts of a zirconyl ammoniumcarbonate solution containing about 10 weight percent zirconium dioxide,about 40 to 75 parts water, and about 5 parts ammonium hydroxide, b.drying the fabric from (a) at about 120*C for about 2 to 3 minutes, c.curing the fabric from (b) at about 130*C for about 2 to 3 minutes, d.washing the fabric from (c), and e. drying the fabric from (d) at about120*C for about 2 to 3 minutes.
 12. A pad bath formulation for producinga pink cellulosic fabric with fungicidal properties, said bathconsisting of about 2 to 4 part of cobalt citrate, about 0.5 to 1.0parts copper metaborate, about 10 to 48 parts of a zirconyl ammoniumcarbonate solution containing about 10 weight percent zirconium dioxide,about 40 to 75 parts water, and about 5 parts ammonium hydroxide.